Synthetic detergent compositions

ABSTRACT

DETERGENT COMPOSITIONS COMPRISING AN ANINIC OR NONIONIC SURFACE ACTIVE AGENT AND A WATER-SOLUBLE SALT OF A COPOLYMER OF 3A,4,5,6,7,7A-HEXAHYDRO-4,7-METHANOINDENE AND MALEIC ANHYDRIDE AS A BUILDER.

United rm. or. end 1/12, 3/26, 7/32 US. Cl. 252541 9 Claims ABSTRACT or ran nrsctosonn Detergent compositions comprising an anionic or nonionie surface active agent and a water-soluble salt of a copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and maleic anhydride as a builder.

BACKGROUND OF THE INVENTION This invention relates to synthetic detergent compositions. More particularly, it relates to the use of the watersoluble organic polymer salts of copolymers of 3a,4,5,6, 7,7a-hexahydro-4,7-methanoindene and maleic anhydride as the builders for synthetic anionic, nonionic and/or amphoteric surface active compounds which are suitable as detergents in aqueous solutions.

As used in the present application, the term builder signifies a substance used with or in a detergent to aid in cleansing.

The trend in the development of modern washing machines is toward full automation. Accompanying this development is the requirement of a detergent which is capable of cleaning all sorts of fibers without damaging them while having an excellent washing capacity with smaller machine power. In general, detergents contain a surface active material, a builder for promoting the functions of said surface active material, and small quantities of substances which protect against recontamination, a bleaching agent, a fluorescent dyestuff, a sizing agent, etc.

As far as the builder for the detergent is concerned, many inorganic builders are known to the art, such as alkali metal carbonates, bicarbonates, phosphates, polyphosphates, borates and silicates, as well as organic builders such as sodium salts of EDTA (ethylenediaminetetraacetic acid) and NTA (nitrilotriacetic acid), among which the most popular is sodium tri-polyphosphate (hereinafter referred to as STP), which is one of the condensation polyphosphates. Condensation polyphosphates such as sodium tripolyphosphate possess an excellent activity as a detergent builder, but, on the other hand, when condensation polyphosphates are mixed with a detergent, they are hydrolyzed under the usual aqueous solution conditions, thus converting them to lower condensation compounds. Hence, they lose their activity as a builder and, thus, deteriorate the detergency efiiciency of the detergent agents. Moreover, when the Waste liquor containing these substances flows into rivers and into sewage water, a great many duckweeds grow to ruin the environmental beauty. In addition, the eifluence of such agents into public waters causes many hazards which have been recently greatly documented. These problems are not solved when utilizing other inorganic and organic builders, because of the disadvantages that these materials have an inferior detergent effect and are not able to produce a detergent composition having excellent detergency efficiency.

One of the objects of the present invention is to provide a novel synthetic detergent composition having an excellent detergent efiiciency and which can be readily disposed without significant environmental or ecological problems,

atent 6 Patented May 1, 1973 thereby overcoming the disadvantages and deficiencies of the prior art compositions.

Another object of the invention is to provide a method for the preparation of the described detergent compositions which may be carried out effectively and advantageously as desired.

These and other objects and advantages of the present invention will become apparent to those skilled in the art from a consideration of the following specification and claims.

SUMMARY OF THE INVENTION t t r t I 1m 1a or C I H (Wt if loo t (I) (II) (III) In the above reaction scheme, Formula III denotes the copolymerized CM-resin.

Advantageously, the process for preparing such a CM- resin is as follows. The 3a,4,5,6,7,7a-hexahydro4,7-methanoindene and maleic anhydride reactants are subjected to radical copolymerization in a molar ratio of 2:8 to 8:2 in the presence or absence of a solvent at a reaction temperature of 50 to 200 C. under a pressure of 1 to 20 kg./cm. or under a reduced pressure. Although it is difiicult to polymerize these reactants separately, a mixture of these monomers as the starting material for a CM-resin undergoes a radical copolymerization relatively easily. As is evident from the above general reaction scheme, the polymerization is eifected on the basis of the reaction of the double bonds of the monomers.

Examples of solvents which may be utilized in the polymerization reaction include carbon tetrachloride, chloroform, dichloromethane, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, tetrachloroethane, tetrachloroethylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, ethyl acetate, dioxane, cyclohexanone, acetonitrile, isopropauol, heptane, octane, kerosene, etc.

The radical initiator employed as the catalyst is added in an amount of from 0.01% to 10% by weight, based on the weight of the monomers. Examples of the radical initiator to be employed include, for example, azo-bisisobutyronitrile, benzoyl peroxide, di-tertiary-butyl peroxide, hydrogen peroxide, lauryl peroxide, dipropionyl peroxide, acetyl peroxide, peracetic acid, perbenzoic acid, tertiary-butyl hydroperoxide, acetylbenzoyl peroxide, diethyl peroxide, urea peroxide, tetraphosphorus peroxide, alkali metal persulfates, alkali metal perborates, alkali metal percarbonates, ammonium persulfate, ammonium perborate, ammonium percarbonate, etc.

An autoclave is employed in the case of the high temperature reaction in a solvent of a lower boiling point. A specific example of preparing a CM-resin to be cmployed in connection with the present invention can be illustrated as follows. 134 parts of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and 98 parts of maleic anhydride are dissolved in 232 parts of acetone and mixed with 2 parts of benzoyl peroxide as a polymerization initiator and the mixture is agitated at 65 C. for 20 hours. After a sufiicient development of the reaction, the reaction mixture is poured in a sufficient quantity of methanol to precipitate the produced copolymer. The recovered copolymer of CM-resin has a molecular weight of 400600 and a saponification value of 350. The yield is 155 parts by weight.

As the CM-resin obtained in this manner is a polybasic acid, it easily forms water-soluble alkali metal salts when dissolved in an aqueous alkaline solution, such as an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution or an aqueous ammonium hydroxide solution. Accordingly, the sodium salt of the CM-resin is easily prepared in a known manner, for example, such as the reaction of a CM-resin with an aqueous sodium hydroxide solution.

In this regard, an example for the preparation of the sodium salt of a CM-resin can be carried out in the following specific manner. A certain volume of 510% sodium hydroxide solution containing 2 moles of NaOH is gradually mixed with 1 mole of the CM-resin with agitation. Then, the resulting mixture is dried by any suitable method, such as by means of vacuum drying, freezedrying, spray-drying, or the like, in order to obtain the sodium salt of the CM-resin.

Not only is the sodium salt utilizable as the builder, but also other water-soluble salts of the CM-resin can be used, such as the potassium salt or the ammonium salt. These water-soluble salts of CM-resin are stable under aqueous solution conditions and do not cause any public hazards, while having a remarkable elfect for preventing recontaminations and cutaneous stimulations. These substances also provide the elfect of preventing an electric charge in articles washed therein. Moreover, it is significant that the CM-resins of the invention are available at less expense in accordance with the development of the petrochemical industry.

The CM-resin utilizable in accordance with this invention are water-soluble CM-resins as discussed above, but in practice the alkali metal salts and/or the ammonium salts of CM-resins are most conveniently and advantageously utilized.

As mentioned above, the technique of the present invention is characterized by utilizing as the builder a watersoluble CM-resin and, therefore, the detergency set forth in the following examples is at least superior to the detergency efficiency of the conventionally employed STP. Furthermore, since the builder of the present invention does not contain phosphorus, solutions containing this builder may be discharged into sewage water without the fear of the growth of duckweeds thus radically eliminating public hazards and other environmental problems.

EXAMPLES OF THE INVENTION The following examples are given merely as illustrative of the present invention and are not to be considered as limiting. Unless otherwise noted, the percentages therein and throughout the application are by weight.

Chosen for the standard soiled fabric specimens employed in these tests were naturally contaminated cloths, which were soiled by rubbing cotton broadcloth #60 against the human skin after desizing. Then the samples were washed in a Terg-O-Tometer at 25 C. and at an article/ detergent solution ratio of 30 for minutes. The reflectance R0 prior to the recontamination of the sample cloth, the reflectance Rs of the contaminated cloth prior to the washing and the reflectance Rw of the contaminated cloth after the washing are measured, respectively. The detergency elficiency D is calculated in accordance with the following formula:

Rw- Rs Example 1 The following detergent solutions are prepared:

Detergent solutions:

(1) Water (2) 0.5% aqueous solutions of the sodium salt of CM- resin (3) 0.04% aqueous solution of a straight chain sodium alkylbenzene sulfonate (an example of an anionic surface active material, hereinafter referred to as LAS) (4) An aqueous solution containing 0.04% of LAS and 0.05% of the sodium salt of the CM-resin (5) An aqueous solution containing 0.04% of LAS and 0.05% of STP The above-mentioned standard soiled fabric specimens are soaked in each of the above detergent solutions and washed at rpm. of said Terg-O-Tometer for 10 minutes. The results obtained are set forth in Table 1.

TABLE 1 Detergency efficiency Detergent solution: D (percent) Water 36.3 0.05% aqueous solution of the sodium of CM-resin 67.8 0.04% solution of LAS 66.0 0.04% solution of LAS+0.05% solution of sodium salt of CM-resin 93.9 0.04% solution of LAS+0.05% solution of STP 93.3

It is evident from these results that the sodium salt of the CM-resin obtained in accordance with the present invention possesses a considerable detergency efiiciency by itself and, furthermore, that a detergent composition containing the same with the builder of the surface active material LAS has a very excellent detergency efiiciency.

Example 2 Employed in the present example are the additive compounds ofpolyoxyethylene nonyl phenyl ether (hereinafter referred to as POENE) with 8 moles and 20 moles of ethylene oxide, respectively (hereinafter referred to as POENE-8 and POENE-20, respectively), as examples of nonionic surface active materials. The following detergent solutions are prepared:

(1) 0.04% aqueous solution of POENE-8 (2) 0.04% aqueous solution of POENE-20 (3) An aqueous solution of 0.04% POENE-8 and 0.05%

CM-resin (4) An aqueous solution of 0.04% POENE-ZO and 0.05

CM-resin Washing is conducted in the same manner and under the same conditions as described in Example 1. The results are shown in Table 2.

The results indicated in Table 2 reveal that the sodium salt of the CM-resin is very effective as a builder for the surface active material POENE.

The CM-resin builders of the present invention show excellent effects not only with LAS and POENE, specifically exemplified above, but also with any conventional surface active material. Hence, the water-soluble salts of CM-resins are effective in connection with detergency efficiency as builders in detergent compositions regardless of the particular type of surface active material employed. Therefore, the present invention offers great technical advantages of obtaining detergents suitable for fully automated washing machines.

The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications as would be obvious to one skilled in the art are intended to be included herein.

We claim:

1. A detergent composition consisting essentially of a surface active agent selected from the group consisting of anionic and nonionic surface active agents, and in an amount effective as a builder, a water-soluble salt of a copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and maleic anhydride.

2. An aqueous solution of the detergent composition according to claim 1.

3. A detergent composition according to claim 1, wherein the ratio of the surface active agent to the builder is about 4:5.

4. A detergent composition according to claim 3, wherein the surface active agent is selected from the group consisting of a straight chain sodium alkylbenzene sulfonate and ethylene oxide adduct of polyoxyethylene nonyl phenyl ether.

5. A detergent composition in accordance with claim 1, wherein said water-soluble salt is an alkali metal or an ammonium salt of said copolymer.

6. A detergent composition in accordance with claim 1, wherein said water-soluble salt is the sodium salt of said copolymer.

7. A detergent composition in accordance with claim 1, wherein said surface active agent comprises a straight chain sodium alkylbenzene sulfonate.

8. A detergent composition in accordance with claim 1, wherein said surface active agent comprises an ethylene oxide adduct of polyoxyethylene nonyl phenyl ether.

9. In a detergent composition consisting essentially of a surface active agent selected from the group consisting of anionic and nonionic surface active agents as a detergent and an effective amount of a builder to aid the efficiency of the detergent, the improvement which comprises a water-soluble salt of a copolymer of 3a,4,5,6,7,7a-hexahydro-4,7-methanoindene and maleic anhydride as a builder, said methanoindene and maliec anhydride being in a molar ratio of about 2:8 to 8:2 respectively.

References Cited UNITED STATES PATENTS 3/1959 Feldmann 252541 X 3/1967 Diehl 252558 X RICHARD D. LOVERING, Primary Examiner 

